Nu-dialkylaminoalkyl alkenyl succinimides



United States Patent 3,018,291 N-DIALKYLAMINOALKYL ALKENYL SUCCINIMIDES Robert G. Anderson, Novato, Frank A. Stuart, Orinda,

where R is an alkenyl radical containing from 30 to 200 carbon atoms, R' is a divalent alkylene radical, and R and R are alkyl radicals. The sum of the carbon atoms in R, R and R is 3 to 10; that is, R, R and R con- 5 tain a total of no more than carbon atoms. i g g gg z h gggggg bgggg gk gi fifiifigzg It is preferred that R is a polymer of an olefin con- Calm, a corporation of Deaware taming from 2 to 5 carbon atoms, wherein the polymer N0 Drawing Filed Aug 24 1959, 335,409 has a molecular weight from 400 to 3000, more par- 3 C (CL 2 0 32 5 ticularly from about 900 to about 1200. Such olefins 10 are exemplified by ethylene, propylene, l-butene, 2-

This invention pertains to a new class of compounds butene, isobutene, and mixtures thereof. Since the methparticularly useful as lubricating oil addition agents. ods of polymerizing the olefins to form polymers thereof These new compounds are N-dialkyl-aminoalkyl alkenyl is immaterial in the formation of the new compound de- Sllccinimides. scribed herein, any of the numerous processes available Alkenyl succinic anhydrides and numerous derivatives can b d h f f are n knqwn the For example, alkeflyl R alkylene radicals include the divalent methylene 235.31% ti it iiifofi 212152iiiiifi ii fiiioitffi 3 1 gs g? f f ig hibitors in lubricating oil compositions. Also, roduets m lca e a m lea S men 6 me 1 obtained by reacting such alkenyl succinic anhydrides propyl It Is pamculaflyz prefenfd that R with monoamines are taught as ferrous corrosion inhibicoinams 3 carbon atoms and that R and R each tors for lubricating oil compositions. tam atom However, the above known alkenyl succinimides are reactants used of the 9 not useful as detergents in lubricating oil compositions. amme rad 1ca1 f the succlfnmlde fdimethylammo In contrast thereto, the alkenyl succinimides described methylamme, dlmethylamlnoethylamme, dlmethylaminoherein are new compounds which are useful as deter- P py dimethylaminobutylamine, dimethylaminogents in lubricating oil compositions. heptylamine, diethylaminomethylamine, diethlaminopro- Thus, it is a primary object of this invention to prepylamine, diethylaminoamylamine, dipropylarninopropylsent as new compounds, alkenyl succinimides which are amine, methylpropylaminoamylamine, propylbutylaminoparticularly useful as detergents in lubricating oil c0methylamine, etc.

POISIUODS. d th th ti h d d The preparation of the monoalkenyl succinimides herezzs z ggg g f sg g gg yf g 5:31 :3 in can be described generally by the following equations, succinimides, are effective lubricating oil addition agents. wherein a polyolefin 1S Ieactedi male-1c anhxfdnd-e The N-dialkylaminoalkyl monoalkenyl succinimides to form the t 5 Suqclmc anhyfinde whlch 18 of this invention are particularly effective as detergents this? reacted with a dlalkyiaimpoalkylilmme to form the in lubricating oil compositions. By the use of lubrifieslred monoalkenyl Succmumde; using eating oil compositions containing these alkenyl i lsobutene as an exampleof the alkenyl radical, and using imides, diesel and gasoline engine parts remain remarkdmqethylammqpropylannne to exemphfy the dlalkyl' ably free of deposits and varnish even under severe op 40 ammoalkylamlnecrating conditions.

The new compounds of this invention, which are fur- I ther described as N-dialkylaminoalkyl monoalkenyl suc- 3 3 3 cinimides wherein the alkenyl radical contains from 30 CH J .CH GH .CH J=CH \oeea to 200 carbon atoms, and wherein said dialkyl amino 1 CH alkyl radical contains a total of 3 to 10 carbon atoms 3 P f can be represented by the formula: 0

wherein n is a number having a value of about 7 to about 50.

The above reaction between a polyolefin and maleic anhydride is an uncatalyzed addition reaction which should not be confused with a copolymerization reaction such as that obtained with a vinyl monomer and maleic anhydride. While the general reaction of an olefin and maleic anhydride is well known for olefins of low molecular weight (e.g., olefins of 18 carbon atoms), no previous work has been done with maleic anhydride and the high molecular weight olefins as described herein.

The reaction set forth and described hereinabove can proceed in a mol ratio of the polyolefin to the maleic anhydride of 1:1 to 1:10; preferably from 1:1 to 1:5. The reaction temperature can vary from 300 F. to 450 F. Because of the greater yield of products obtained thereby, it is preferred to use the higher temperature range (e.g., 375 F. to 450? F.).

, In the second step of the reaction as exemplified by Equation II hereinabove, the yield of the imide is extremely high even though the reactants are used in equal molar ratios.

The reaction described by Equation II hereinabove can be made at 220 F. to 500 F., preferably from 300 F. to 400? F. The alkenyl succinic anhydride and the polyamine are reacted in about equal molar quantities. An excess of the amine can be used, and the unreacted amine removed by distillation.

Since the reaction between the polyolefin and maleic anhydride may not go to completion, the resulting alkenyl succinic anhydride may contain some unreacted polyolefin. As it may not be desirable to separate out this unreacted polyolefin at this stage, the resulting imide formed by reaction of the alkenyl succinic anhydride and the diamine will contain this polyolefin as an impurity which can be a diluent in the formation of lubricating oil compositions. However, if it is so desired, this unreacted polyolefin can be removed by precipitation, for example, by acetone or methanol from a hydrocarbon solution.

The preparation of the alkenyl succinimides of dialkylamino alkyl amine is illustrated in the following examples.

EXAMPLE I.PREPARATION OF POLYBUTENYL SUCCINIC ANHYDRIDE A mixture of 1000 grams (1 mol) of a polybutene having a molecular weight of about 1000 and 98 grams (1 mol) of maleic anhydride was heated at 410 F. in a nitrogen atmosphere with agitation for a period of 24 hours. The reaction mixture was cooled to 150 F., and 700 cc. of hexane added; after which the mixture was filtered under vacuum. After vacuum distillation to remove the hexane from the filtrate, the product was maintained at 350 F. at an absolute pressure of 10 mm. Hg for one hour to remove traces of maleic anhydride. The crude polybutenyl succinic anhydride thus prepared had a saponification number of 79.

EXAMPLE H.--PREPARATION OF N-DIMETHYL- AMINOPROPYL POLYBUTENYL SUCCINIMIDE A mixture of 21.3 grams (0.21 mol) of dimethylaminopropylamine and 150 grams (0.09 mol) of the polybutenyl succinic anhydride of Example I hereinabove, was blended with agitation in a nitrogen atmosphere, and the mixture washeated at 500 F. for a period of one hour, after which the absolute pressure was reduced to about 200 mm. Hg at this temperature during a period of 30 minutes to facilitate the removal of water and excess amine. The reaction mixture was then allowed to reach room temperature at this reduced pressure. The reaction product contained 1.7% nitrogen (theory=1.8%). The identity of mides. The polyamine was a dimethylaminopropylamine, and the alkenyl radical on the alkenyl succinimide was a polybutene, the molecular weight of which is noted in Table I.

As lubricating oil additives, these alkenyl succinimides can be used in amounts of 0.1% to by weight; preferably 0.25% to 5% by weight.

Table II hereinbelow sets forth data showing the effectiveness of the new compounds of this invention as lubricating oil additives.

The monoalkenyl succinimide used was an N-dimethylaminopropyl alkenyl succinimide wherein the alkenyl radical had a molecular weight of approximately 1000, which alkenyl radical was a polymer of isobutene.

The base oil was anSAE 10 base oil.

The data were obtained in a caterpillar L-l test under Mil-L-2104 conditions for 120 hours.

The PD Nos. refer to the piston discoloration rating. After the engine test the three piston lands are examined visually. To a piston land which is completely black is assigned a PD number of 800; to one which is completely clean, a PD number of 0; to those intermediate between completely black and completely clean are assigned PD numbers intermediate in proportion to the extent and degree of darkening.

The GD Nos. refer to the percentage deposits in the piston ring grooves; and 0 evaluation being a clear groove; and a number of being a groove full of deposits.

Table II Additive A B succinimide, Wt. percent 1. 5 0. 0 Test R sults:

G!) No 2 39 PD No 80,0,0 800,800,800

agents, etc. I

We claim: 1. The compound represented by the formula:

RCHC /R /N-RN CH2C\ R wherein R is a polyisobutylene radical of from 30 to 200 carbon atoms, R is a divalent alklyene radical of from 1 to 3 carbon atoms, R and R are alkyl radicals of from 1 to 3 carbon atoms, and R, R and R combined con. tain a total of no more than 10 carbon atoms.

5 6 2. The compound bon atoms which polyolefin is a polymer of an olefin of CH3 CH3 CH3 1 I Hs-CCH2CH:C CH=COH2OHC\ /OH3 (5H3 /n /NCH:CH2CH2N cH2o CH3 wherein n is a number having a value of about 7 to about from 2 to 5 carbon atoms, R is a divalent alkylene radical 50. 0 of from 1 to 3 carbon atoms, R and R are alkyl radicals 3. The compound of the formula: of from 1 to 3 carbon atoms, and R, R and R como bined contain a total of no more than 10 carbon atoms. RCH--C N R References Cited in the file of this patent UNITED STATES PATENTS 0 2,540,800 Trigg et al. Feb. 5, 1951 wherein R is a polyolefin radical of from to 200 car- 2,638,450 White et a1. May 12, 1953 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N0a 3 Ol8 29l January 28 'l962 Robert G. Anderson et alt It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, the end of the printed equation should appear as shown below instead of as in the patent:

o on-0 CH3 \NCH2CH2CH2=N/ CH2==C CH3 Signed and sealed thisv 5th day of June 1962,

(SEAL) Attest:

ERNEST W, SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. THE COMPOUND REPRESENTED BY THE FORMULA: 